论文部分内容阅读
标题化合物（Ｍｅ_２ＳｉＳｉＭｅ_２）［η￣５－（３－Ｍｅ_３ＳｉＣ_５Ｈ_３）Ｆｅ（ＣＯ）_２］_２／（μ－ＣＯ）_２（Ａ）分子中的Ｆｅ－Ｆｅ键被钠汞齐还原断裂，生成相应的双铁负离子，分别与ＭｅＣＯＣｌ、ＰｈＣＯＣｌ、ＰｈＣＨ_２Ｃｌ、ＣｌＣＨ_２ＣＯＯＣ_２Ｈ_５和Ｐｈ_３ＳｎＣｌ进行亲核取代反应，生成在铁原子上引入相应取代基的产物（Ｍｅ_２ＳｉＳｉＭｅ_２）［η￣５－（３－Ｍｅ_３ＳｉＣ_５Ｈ_３）Ｆｅ（ＣＯ）_２Ｒ］_２（Ｒ：ＭｅＣＯ（１），ＰｈＣＯ（２），ＰｈＣＨ_２（３），ＣＨ_２ＣＯＯＣ_２Ｈ_５（４），Ｐｈ_３Ｓｎ（５），Ｉ（６））。Ａ在氯仿中与碘反应，得到Ｆｅ－Ｆｅ断裂的双铁碘化物，但在苯中与过量碘反应，则得到Ｆｅ－Ｉ－Ｆｅ桥联的离子型化合物（Ｍｅ_２ＳｉＳｉＭｅ_２）［η￣５－（３－Ｍｅ_３ＳｉＣ_５Ｈ_３）Ｆｅ（ＣＯ）_２］_２Ｉ·Ｉ（７）。化合物６的晶体和分子结构经Ｘ射线衍射测定，６属单斜晶系，Ｐ２１／ｃ空间群，ａ＝１．７２１７（４）ｎｍ，ｂ＝０．７７５３（２）ｎｍ，Ｃ＝１．３６２９（７）ｎｍ，β＝１０３．８０（３）°，Ｖ＝１．７６７（２）ｎｍ３，Ｚ＝４，Ｄｃ＝１．６２９９·ｃｍ－１，最终偏差因子Ｒ＝０．０５４。
The Fe-Fe bond in the molecule of the title compound (Me_2SiSiMe_2) [η¯5- (3-Me_3SiC_5H_3) Fe (CO) _2] _2 / (μ-CO) _2 (A) is reduced by sodium amalgam to form the corresponding bis (3-Me3SiC_5H_3) Fe (CO) _2R], which were introduced into the corresponding substituents on the iron atom, respectively, by the nucleophilic substitution reactions with FeCl3, FeCl3, FeCl3, ClCH2COOC_2H_5 and Ph_3SnCl, _2 (R: MeCO (1), PhCO (2), PhCH_2 (3), CH_2COOC_2H_5 (4), Ph_3Sn (5), I (6)). A reaction with iodine in chloroform to give Fe-Fe double iron iodide cleavage, but with excess iodine in benzene reaction, then get Fe-I-Fe bridged ionic compounds (Me_2SiSiMe_2) [η ~ 5- ( 3-Me_3SiC_5H_3) Fe (CO) _2] _2I · I (7). The crystal structure and molecular structure of compound 6 were determined by X-ray diffraction. There were 6 monoclinic and P21 / c space groups, a = 1.7217 (4) nm and b = 0.7753 (2) nm, respectively. 3629 (7) nm, β = 103.80 (3) °, V = 1.767 (2) nm3, Z = 4 and Dc = 1.6299 · cm-1. The final deviation factor R = 0.054.